Liquid hardening

Abstract

Curing agents for air-drying alkyd-based resins, coatings, such as paint, varnish or wood stain, inks and linoleum floor coverings, based on an iron/manganese complex containing tetradentate, pentadentate or hexadentate nitrogen donor ligands are disclosed.

What is claimed is: 
     
       1. A curable liquid medium comprising:
 a) from 1 to 90 wt % of an alkyd-based resin; and, 
 b) from 0.0001 to 0.1 wt % of a siccative, wherein the siccative is an iron or manganese complex of a tetradentate, pentadentate or hexadentate nitrogen donor ligand, wherein the ligand is selected from the group consisting of N-methyl-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; 
 N-octyl-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; N-octadecyl-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; 
 N-methyl-N,N′,N′-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; 
 N-ethyl-N,N′,N′-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; 
 N-methyl-N,N′,N′-tris(5-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; 
 N-ethyl-N,N′,N′-tris(5-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; 
 N-benzyl-N,N′,N′-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; 
 N-benzyl-N,N′,N′-tris(5-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; 
 N-butyl-N,N′,N′-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; 
 N-octyl-N,N′,N′-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; 
 N-dodecyl-N,N′,N′-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; 
 N-octadecyl-N,N′,N′-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; 
 N-methyl-N,N′,N′-tris(imidazol-2-ylmethyl)ethylenediamine; 
 N-ethyl-N,N′,N′-tris(imidazol-2-ylmethyl)ethylenediamine; 
 N,N′-dimethyl-N,N′-bis(imidazol-2-ylmethyl)ethylenediamine; 
 N-(1-propan-2-ol)-N,N′,N′-tris(imidazol-2-ylmethyl)ethylenediamine; 
 N-(1-propan-2-ol)-N,N′,N′-tris(1-methyl-imidazol-2-ylmethyl)ethylenediamine; 
 N,N-diethyl-N′,N″,N″-tris(5-methyl-imidazol-4-ylmethyl)-diethylenetriamine; 
 N-(3-propan-1-ol)-N,N′,N′-tris(1-methyl-imidazol-2-ylmethyl)ethylenediamine; 
 N-hexyl-N,N′,N′-tris(imidazol-2ylmethyl)-ethylenediamine; 
 N-methyl-N,N′,N′-tris(benzimidazol-2ylmethyl)ethylenediamine; and 
 N-(3-propan-1-ol)methyl-N,N′,N′-tris(benzimidazol-2ylmethyl)ethylenediamine. 
 
     
     
       2. The curable liquid medium according to  claim 1 , wherein the iron ion is selected from the group consisting of Fe(II) and Fe(III). 
     
     
       3. The curable liquid medium according to  claim 1 , wherein the manganese ion is selected from the group consisting of Mn(II), Mn(III), and Mn(IV). 
     
     
       4. The curable liquid medium according to  claim 1 , wherein the siccative is an iron (II) or iron (III) complex. 
     
     
       5. The curable liquid medium according to  claim 4 , wherein the siccative is an iron (II) complex. 
     
     
       6. The curable liquid medium according to  claim 1 , wherein the content of the siccative is between 0.0001 and 0.5% w/w. 
     
     
       7. The curable liquid medium according to  claim 1  further comprising 0.001% and 0.1% of at least one antioxidant selected from the group consisting of di-tert-butyl hydroxy toluene, ethoxyquine, α-tocopherol, and 6-hydroxy-2,5,7,8-tetra-methylchroman-2-carboxylic acid. 
     
     
       8. The curable liquid medium according to  claim 7 , wherein the composition comprises between 0.002 and 0.05% of at least one antioxidant. 
     
     
       9. The curable liquid medium according to  claim 7 , wherein the antioxidant is α-tocopherol. 
     
     
       10. The curable liquid medium according to  claim 1 , wherein the medium contains between 0.001 and 90 wt % of ethylene glycol, diethylene glycol, dipropylene glycol, glycerol, pentaerythritol, dipenta erythritol, neopentyl glycol, trimethylol propane, trimethylol ethane, di-trimethylol propane and 1,6-hexane diol. 
     
     
       11. The curable liquid medium according to  claim 10 , wherein the medium contains between 0.1 and 50 wt % of ethyleneglycol or glycerol. 
     
     
       12. The curable liquid medium according to  claim 10 , wherein the medium contains between 0.3 and 5 wt % of ethyleneglycol or glycerol. 
     
     
       13. The curable liquid medium according to  claim 1 , containing between 0.001 and 2.5% of lead, zirconium, bismuth, barium, vanadium, cerium, calcium, lithium, strontium, and zinc. 
     
     
       14. The curable liquid medium according to  claim 1  when cured. 
     
     
       15. The curable liquid medium according to  claim 1 , wherein the medium is selected from the group consisting of a paint, a varnish, a wood stain, an ink, and a linoleum floor covering. 
     
     
       16. The curable liquid medium according to  claim 15 , wherein the ink is selected from the group consisting of a metal plate ink, a lithographic ink, a relief printing ink, a screen ink, and an offset overprinting ink. 
     
     
       17. The curable liquid medium according to  claim 1 , wherein the medium further comprises at least one binder selected from the group consisting of polyacrylates binder and a polyurethane binder.